US20090057613A1 - Fluorescent quinacridones - Google Patents

Fluorescent quinacridones Download PDF

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US20090057613A1
US20090057613A1 US11/630,488 US63048805A US2009057613A1 US 20090057613 A1 US20090057613 A1 US 20090057613A1 US 63048805 A US63048805 A US 63048805A US 2009057613 A1 US2009057613 A1 US 2009057613A1
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alkyl
group
substituted
phenyl
alkoxy
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Hiroshi Yamamoto
Norihisa Dan
Paul Adriaan Van Der Schaaf
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BASF Schweiz AG
BASF Corp
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Ciba Spezialitaetenchemie Holding AG
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    • H—ELECTRICITY
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    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO

Definitions

  • the present invention relates to compounds of the formula
  • a luminescent device comprising a composition according to the present invention is high in the efficiency of electrical energy utilisation and high in luminance.
  • U.S. Pat. No. 6,280,859 relates to a light-emitting material, for example a quinacridone derivative, and an organic EL device for which the light-emitting material is adapted.
  • a light-emitting material for example a quinacridone derivative
  • an organic EL device for which the light-emitting material is adapted.
  • the following quinacridone derivatives are explicitly mentioned:
  • EP-A-0939972 relates to an electroluminescent device comprises an electroluminescent element comprising a hole injection and/or hole transport zone containing an optionally substituted tris-1,3,5-(aminophenyl)benzene compound, a luminescent material and a quinacridone derivative.
  • the quinacridone derivative is not a quinacridone substituted by a group —NAr 1 Ar 2 .
  • US200210038867A1 relates to an organic EL device comprising a light emitting layer containing a specific coumarine derivative and a specific quinacridone compound and a hole injecting layer and/or transporting layer containing a specific tetraaryidiamine derivative.
  • the quinacridone compound is not a quinacridone substituted by a group —NAr 1 Ar 2 .
  • luminescent devices which are high in the efficiency of electrical energy utilisation and high in luminance, can be obtained if specific quinacridone compounds or specific combinations of quinacridone and, for example, diketopyrrolopyrrole (DPP) compounds are used, especially as light emitting substances.
  • DPP diketopyrrolopyrrole
  • the present invention relates to quinacridone compounds of formula
  • R 1 and R 2 may be the same or different and are selected from a C 1 -C 25 alkyl group, which can be substituted by fluorine, chlorine or bromine, an allyl group, which can be substituted one to three times with C 1 -C 4 alkyl, a cycloalkyl group, a cycloalkyl group, which can be condensed one or two times by phenyl which can be substituted one to three times with C 1 -C 4 -alkyl, halogen, nitro or cyano, an alkenyl group, a cycloalkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group, a haloalkynyl group, a ketone or aldehyde group, an ester group, a carbamoyl group, a ketone group, a silyl group, a siloxanyl group, A 3 or —CR 7 R 8
  • R 7 and R 8 independently from each other stand for hydrogen, or C 1 -C 4 alkyl, or phenyl, which can be substituted one to three times with C 1 -C 4 alkyl
  • a 3 stands for aryl or heteroaryl, in particular phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy
  • m stands for 0, 1, 2, 3 or 4
  • R 3 , R 3′ , R 6 and R 6′ independently of one another, represent hydrogen, halogen, C 1 -C 18 alkyl, halogen-substituted C 1 -C 18 alkyl, C 1 -C 18 alkoxy, C 1 -C 18- aalkylthio, cycloalkyl, optionally substituted aryl or arylalkyl, wherein the substituents are alkoxy, halogen or alkyl, R 4 and R 4′
  • R 5′ and R 6′ and/or R 5 and R 6 together are a group
  • R 30 , R 31 , R 32 and R 33 are independently of each other hydrogen, C 1 -C 18 alkyl, halogen-substituted C 1 -C 18 alkyl, C 1 -C 18 alkoxy, or C 1 -C 28 alkylthio
  • R 34 , RF, R 36 and R 37 are independently of each other hydrogen, C 1 -C 18 alkyl, halogen-substituted C 1 -C 18 alkyl, C 1 -C 18 alkoxy, or C 1 -C 28 alkylthio
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently of each other an aryl group, which can optionally be substituted, or a heteroaryl group, which can optionally be substituted, with the proviso that at least one of the groups R 4 , R 4′ , R 5 and R 5′ is a group —NAr 1 Ar 2 , or —NAr 3 Ar 4 , and compounds of formula
  • R 1 , R 2 , R 3 , R 3′ , R 4 , R 4′ , R 6 , R 6′ , Ar 1 , A 2 Ar 3 and Ar 4 are as defined above.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are preferably independently of each other a group —Ar 5 —X 1 —Ar 6 ,
  • X 1 is C(X 2 )(X 3 , —O—, —S—, —SO 2 —, —C( ⁇ O)—,
  • X 2 and X 3 independently from each other stand for hydrogen, C 1 -C 18 alkyl, halogen-substituted C 1 -C 18 alkyl, or phenyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy
  • X 4 stands for C 1 -C 18 alkyl, halogen-substituted C 1 -C 18 alkyl, or phenyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy
  • R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 4 and R 45 independently from each other stands for hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, or phenyl.
  • R 1 , R 2 , Ar 1 , Ar 2 , Ar 3 and Ar 4 are as defined above.
  • the groups —NAr 1 Ar 2 , or —NAr 3 Ar 4 can be different, but have preferably the same meaning.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently of each other a group
  • R 38 , R 39 , R 40 , and R 41 are as defined above, especially phenyl, tolyl, 2-naphthyl, and 1-naphthyl.
  • R 42 , R 43 , R 44 , and R 45 are as defined above, especially
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently of each other a group —Ar 5 —X 1 —Ar 6 , particularly preferred examples of Ar 1 , Ar 2 , Ar 3 and Ar 4 are a group
  • R 38 is hydrogen, or C 1 -C 4 alkyl
  • R 1 and R 2 may be the same or different and are preferably selected from a C 1 -C 18 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl; a C 5 -C 12 cycloalkyl group, especially cyclohexyl, which
  • R 51 , R 52 and R 53 are independently of each other hydrogen, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen and cyano; a C 5 -C 12 cycloalkenyl group, especially cyclohexenyl, which can be substituted one to three times with C 1 -C 4 -alkyl, or C 1 -C 4 -alkoxy; a C 6 -C 14 aryl group, especially phenyl, biphenylyl, 1- or 2-naphthyl, which can be substituted one to three times by C 1 -C 8 alkyl, or C 1 -C 8 alkoxy; or —CR 7 R 8 —(CH 2 ) m -A 3 wherein
  • R 7 and R 8 stand for hydrogen, or C 1 -C 4 alkyl
  • a 3 stands for phenyl, 1- or 2-naphthyl, which can be substituted one to three times by C 1 -C 8 alkyl, or C 1 -C 8 alkoxy
  • m stands for 0, or 1.
  • R 1 and R 2 are independently of each other C 1 -C 8 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl;
  • R 11 is hydrogen, or methyl
  • R 12 is hydrogen, or methyl
  • a 5 is
  • R 5 , R 6 and R 7 are independently of each other hydrogen, C 1 -C 4 -alkyl, phenyl or halogen, wherein groups
  • R 5 , R 6 and R 7 are hydrogen; R 6 is C 1 -C 4 -alkyl, phenyl and R 5 and R 7 are hydrogen; R 5 is C 1 -C 4 -alkyl and R 6 and R 7 are hydrogen; or R 5 is hydrogen and R 5 and R 7 are C 1 -C 4 -alkyl are most preferred.
  • a further preferred embodiment of the present invention is directed to compositions comprising a guest chromophore and a host chromophore, wherein the absorption spectrum of the guest chromophore overlaps with the fluorescence emission spectrum of the host chromophore, wherein the host chromophore is a diketopyrrolopyrrole having a photoluminescence emission peak at 500 to 720 nm, preferably 520 to 630 nm, most preferred 540 to 600 nm and wherein the guest chromophore is a compound of formula I.
  • Such diketopyrrolopyrrole compounds are, for example, described in EP-A-1087005, EP-A-1087006, WO03/002672, WO031022848, WO03064558 and WO2004/090046.
  • the host chromophore is preferably a diketopyrrolopyrrole (“DPP”) represented by formula
  • R 13 and R 14 independently from each other stand for C 1 -C 25 alkyl, which can be substituted by fluorine, chlorine or bromine, C 5 -C 12 -cycloalkyl or C 5 -C 12 cycloalkyl which can be condensed one or two times by phenyl which can be substituted one to three times with C 1 -C 4 -alkyl, halogen, nitro or cyano, silyl, A 6 or —CR 11 R 12 —(CH 2 ) m -A 6 , wherein R 11 and R 12 independently from each other stand for hydrogen, fluorine, chlorine, bromine, cyano or C 1 -C 4 alkyl, which can be substituted by fluorine, chlorine or bromine, or phenyl which can be substituted one to three times with C 1 -C 4 alkyl, A 6 stands for phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alky
  • R 25 , R 26 , R 27 independently from each other stands for hydrogen, C 1 -C 25 -alkyl, —CR 11 R 12 —(CH 2 ) m -A 6 , cyano, halogen, —OR 29 , —S(O) p R 30 , or phenyl, which can be substituted one to three times with C 1 -C 8 alkyl or C 1 -C 8 alkoxy, wherein RF stands for C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl, —CR 11 R 12 —(CH 2 ) m —Ph, C 6 -C 24 -aryl, or a saturated or unsaturated heterocyclic radical comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, R 30 stands for C 1 -C 25 -alkyl, C 5 -C 12
  • R 13 and R 14 independently of each other stand, preferably, for C 1 -C 8 alkyl, C 5 -C 12 -cycloalkyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or —CR 11 R 12 —(CH 2 ) m -A 6 wherein R 11 and R 12 stand for hydrogen, A 6 stands for phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, and m stands for 0 or 1.
  • a 4 and A 5 independently from each other stand, preferably, for
  • R 25 is C 1 -C 8 -alkyl, phenyl, 1- or 2-naphthyl.
  • the host chromophore is alternatively a “heterocyclic” diketopyrrolopyrrole (“DPP”) described in WO2004/090046, especially a diketopyrrolopyrrole (“DPP”) represented
  • R 53 and R 54 may be the same or different and are selected from a C 1 -C 25 alkyl group, which can be substituted by fluorine, chlorine or bromine, an allyl group, which can be substituted one to three times with C 1 -C 4 alkyl, a cycloalkyl group, or a cycloalkyl group, which can be condensed one or two times by phenyl which can be substituted one to three times with C 1 -C 4 -alkyl, halogen, nitro or cyano, an alkenyl group, a cycloalkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group, a haloalkynyl group, a ketone or aldehyde group, an ester group, a carbamoyl group, a ketone group, a silyl group, a siloxanyl group, A 8 or —CR 60
  • R 55 is a hydrogen atom, a C 1 -C 2 alkyl group, a C 1 -C 8 alkoxy group, a group of formula
  • R 57 , R 58 and R 59 independently from each other stands for hydrogen, C 1 -C 8 -alkyl, or C 1-8 -alkoxy, and R 56 stands for hydrogen, or C 1 -C 8 -alkyl.
  • R 53 and RF independently from each other are selected from C 1 -C 14 alkyl, C 5 -C 12 -cycloalkyl, especially cyclohexyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or C 5 -C 12 -cycloalkyl, especially cyclohexyl, which can be condensed one or two times by phenyl, which can be substituted one to three times with C 1 -C 4 -alkyl, halogen, nitro or cyano, phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or —CR 60 R 61 —(CH 2 ) m -A 8 wherein R 60 and R 61 stand for hydrogen, A 8 stands for phenyl or 1- or 2-naphthyl, which can be substitute
  • DPP compounds represented by the formula III or IV, which are listed below:
  • a 4 A 5
  • R 13 R 14 H-1 H-2 CH 3 , H-3 H-4 CH 3 , H-5 —CH(CH 3 ) 2 H-6 —(CH 2 ) 3 CH 3 H-7 H-8 —Si(CH 3 ) 3 H-9 H-10 H-11 H-12 H-13 —CH(CH 3 ) 2 H-15 H-16 H-16 H-17 —CH(CH 3 ) 2 H-18 H-19 H-20 H-21 H-22 —CH 3 H-23 —CH(CH 3 ) 2 H-24 H-25 n-C 12 H 25 H-26 —CH 2 F H-27 H-28 H-29
  • a 6 A 7
  • R 53 R 54 H-30 —CH 3 H-31 —CH(CH 3 ) 2 H-32 H-33 —CH 3 H-34 —CH(CH 3 ) 2 H-35 —CH 3 H-36 —CH 3 H-37 —CH(CH 3 ) 2 H-38 —CH 3 H-39 —
  • the weight ratio of the host chromophore to the guest chromophore is in general 50:50 to 99.99:0.01, preferably 90:10 to 99.99:0.01, more preferably 95:5 to 99.9:0.1, most preferred 98:2 to 99.9:0.1.
  • compositions comprise and the derivatives thereof, Znq 2 , Zn(OX) 2 , Zn(BTZ) 2 , BeBq 2 , Be(5Fla) 2 , Balq 2 , AJPh 3 , Zn(ODZ) 2 , Zn(TDZ) 2 , Zn(PhPy) 2 , Zn(BIZ), Alpq 3 , Al(ODZ) 3 , Zn(NOD) 2 , Zn(Phq) 2 , or Zn(NOOD) 2 as host and the quinacridone compounds of formula (I) as guest.
  • the host/guest compositions can be optionally used with other known fluorescent compounds as an additional dopant, for example, fused derivatives of aromatic hydrocarbons such as rubrene and perylene; fused heterocyclics such as pyridinothiadiasole, pyrazolopyridine and naphtalimide derivatives; rare earth complexes, such as Eu, Ir, or Pt complexes; zincporphyrin, rhodamine, deazaflavin derivatives, coumarine derivatives, phenoxazones, quinacridones, dicyanoethenylarenes, or the pyrromethene metal complexes disclosed in EP-A-1,253,151, JP2001 257077, JP2001 257078, and JP2001 297881.
  • Compounds of formula I can be prepared by a process, which comprises reacting a quinacridone compound
  • R 4 , R 4′ , R 5 and R 6 is halogen, preferably Cl, or Br, with a nucleophilic agent HNAr 1 Ar 2 in the presence of an (anhydrous) organic solvent, such as, for example o-xylene, and of an (anhydrous) base, such as, for example, sodium tert-butoxide, at a temperature in the range of from usually 100 to 220° C. optionally in the presence of a catalyst as described, for example, in WO99/47474, such as, for example, [(allyl)PdBr(P(iPr) 3 )].
  • an (anhydrous) organic solvent such as, for example o-xylene
  • an (anhydrous) base such as, for example, sodium tert-butoxide
  • the compounds of formula V can be prepared by reacting compounds of formula
  • halogen compound R 1 —X wherein at least one of the groups R 4 , R 4′ , R 5 and R 5′ is halogen, preferably 1, or Br, in the presence of a base, such as, for example, sodium hydride, in an organic solvent, such as, for example, dry N-methylpyrrolidone (NMP).
  • a base such as, for example, sodium hydride
  • NMP dry N-methylpyrrolidone
  • the compounds of formula VI are commercially available, such as, for example C. I. Pigment Red 202, or C.I. Pigment Red 209, or can be prepared according to or in analogy to procedures known in the state of the art, see, for example EP-A-933972.
  • halogen means fluorine, chlorine, bromine and iodine.
  • C 1 -C 25 alkyl is typically linear or branched—where possible—methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl, preferably C 1 -C 8 al
  • haloalkyl or halogen-substituted alkyl
  • haloalkenyl and haloalkynyl mean groups given by partially or wholly substituting the above-mentioned alkyl group, alkenyl group and alkynyl group with halogen, such as trifluoromethyl etc.
  • aldehyde group, ketone group, ester group, carbamoyl group and amino group include those substituted by an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the heterocyclic group may be unsubstituted or substituted.
  • sil group means a group of formula —SiR 62 R 63 R 64 , wherein R 62 , R 63 and R 64 are independently of each other a C 1 -C 8 alkyl group, in particular a C 1 -C 4 alkyl group, a C 6 -C 24 aryl group or a C 7 -C 12 aralkylgroup, such as a trimethylsilyl group.
  • siloxanyl group means a group of formula —O—SiR 62 R 63 R 64 , wherein R 2 , R 63 and R 64 are as defined above, such as a trimethylsiloxanyl group.
  • C 1 -C 8 alkoxy examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tart.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C 1 -C 4 alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy.
  • alkylthio group means the same groups as the alkoxy groups, except that the oxygen atom of ether linkage is replaced by a sulfur atom.
  • aryl group is typically C 8 -C 24 aryl, such as phenyl, pentalenyl, indenyl, azulenyl, 1-naphthyl, 2-naphthyl, 4-biphenylyl, as-indacenyl, s-indacenyl, acenaphthylenyl, phenanthryl, terphenyl, pyrenyl, 2- or 9-fluorenyl, fluoranthenyl, acephenanthrylenyl, aceanthrylenyl, triphenylenyl, pyrenyl, or anthracenyl, preferably C 6 -C 12 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, which may be unsubstituted or substituted.
  • aralkyl group is typically C 7 -C 24 aralkyl, such as benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenyl-butyl, ⁇ , ⁇ -dimethyl- ⁇ phenyl-butyl, ⁇ -phenyl-dodecyl, ⁇ -phenyl-octadecyl, ⁇ -phenyl-eicosyl or ⁇ -phenyl-docosyl, preferably C 7 -C 18 aralkyl such as benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenyl-butyl, ⁇ , ⁇ -dimethyl-phenyl-butyl, ⁇ -phenyl-dodecyl or ⁇ -phenyl-octade
  • aryl ether group is typically a C 6-24 aryloxy group, that is to say O—C 6-24 aryl, such as, for example, phenoxy or 4-methoxyphenyl.
  • aryl thioether group is typically a C 6-24 arylthio group, that is to say S—C 6-24 aryl, such as, for example, phenylthio or 4-methoxyphenylthio.
  • carbamoyl group is typically a C 1-18 carbamoyl radical, preferably C 1-8 carbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl, dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.
  • cycloalkyl group is typically C 5 -C 12 cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted.
  • cycloalkenyl group means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be unsubstituted or substituted.
  • the cycloalkyl group in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with C 1 -C 4 -alkyl, halogen and cyano. Examples of such condensed cyclohexyl groups are:
  • R 51 , R 52 , R 53 , R 54 , R 55 and R 58 are independently of each other C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen and cyano, in particular hydrogen.
  • heteroaryl or heterocyclic group is a ring with five to seven ring atoms, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic radical with five to 18 atoms having at least six conjugated ⁇ -electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl
  • aryl and “alkyl” in alkylamino groups, dialkylamino groups, alkylarylamino groups, arylamino groups and diarylgroups are typically C 1 -C 25 alkyl and C 6 -C 24 aryl, respectively.
  • the above-mentioned groups can be substituted by a C 1 -C 8 alkyl, a hydroxyl group, a mercapto group, C 1 -C 8 alkoxy, C 1 -C 8 alkylthio, halogen, halo-C 1 -C 8 alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, or a siloxanyl group.
  • the present invention relates further to an electroluminescent device having the compounds of formula I or the compositions according to the present invention between an anode and a cathode and emitting light by the action of electrical energy.
  • an anode/a hole transporting layer/an electron transporting layer/a cathode in which the compounds or compositions of the present invention are used either as positive-hole transport compound or composition, which is exploited to form the light emitting and hole transporting layers, or as electron transport compounds or compositions, which can be exploited to form the light-emitting and electron transporting layers, (ii) an anode/a hole transporting layer/a light-emitting layer/an electron transporting layer/a cathode, in which the compounds or compositions form the light-emitting layer regardless of whether they exhibit positive-hole or electron transport properties in this constitution, (iii) an anode/a hole injection layer/a hole transporting layer/a light-emitting layer/an electron transporting layer/a cathode, (iv) an anode/a hole transporting layer/a light-emitting layer/a positive hole inhibiting layer/an electron transporting layer/a cathode, (v) an anode/a hole injection
  • the compounds and compositions of the present invention can, in principal, be used for any organic layer, such as, for example, hole transporting layer, light emitting layer, or electron transporting layer, but are preferably used as the light emitting material in the light emitting layer.
  • Thin film type electroluminescent devices usually consist essentially of a pair of electrodes and at least one charge transporting layer in between.
  • a hole transporting layer (next to the anode) and an electron transporting layer (next to the cathode) are present Either one of them contains—depending on its properties as hole-transporting or electron-transporting material—an inorganic or organic fluorescence substance as light-emitting material. It is also common, that a light-emitting material is used as an additional layer between the hole-transporting and the electron-transporting layer.
  • a hole injection layer can be constructed between an anode and a hole transporting layer and/or a positive hole inhibiting layer can be constructed between a light emitting layer and an electron transporting layer to maximise hole and electron population in the light emitting layer, reaching large efficiency in charge recombination and intensive light emission.
  • the devices can be prepared in several ways. Usually, vacuum evaporation is used for the preparation.
  • the organic layers are laminated in the above order on a commercially available indium-tin-oxide (“ITO”) glass substrate held at room temperature, which works as the anode in the above constitutions.
  • ITO indium-tin-oxide
  • the membrane thickness is preferably in the range of 1 to 10,000 nm, more preferably 1 to 5,000 nm, more preferably 1 to 1,000 nm, more preferably 1 to 500 nm.
  • the cathode metal such as a Mg/Ag alloy, a binary Li—Al or LiF—Al system with an thickness in the range of 50-200 nm is laminated on the top of the organic layers.
  • the vacuum during the deposition is preferably less than 0.1333 Pa (1 ⁇ 10 ⁇ 3 Torr), more preferably less than 1.333 ⁇ 10 ⁇ 3 Pa (1 ⁇ 10 ⁇ 5 Torr), more preferably less than 1.333 ⁇ 10 ⁇ 4 Pa (1 ⁇ 10 ⁇ 7 Torr).
  • anode materials which possess high work function such as metals like gold, silver, copper, aluminum, indium, iron, zinc, tin, chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungsten and the like, metallic alloys such as magnesium/copper, magnesium/silver, magnesium/aluminum, aluminum/indium and the like, semiconductors such as Si, Ge, GaAs and the like, metallic oxides such as indium-tin-oxide (“ITO”), ZnO and the like, metallic compounds, such as CuI and the like, and furthermore, electroconducting polymers, such as polyacetylene, polyaniline, polythiophene, polypyrrole, polyparaphenylene and the like, preferably ITO, most preferably ITO on glass as substrate can be used.
  • metallic alloys such as magnesium/copper, magnesium/silver, magnesium/aluminum, aluminum/indium and the like, semiconductors such as Si, Ge, GaAs and the like,
  • metals, metallic alloys, metallic oxides and metallic compounds can be transformed into electrodes, for example, by means of the sputtering method.
  • the electrode can be formed also by the vacuum deposition method.
  • the electrode can be formed, furthermore, by the chemical plating method (see for example, Handbook of Electrochemistry, pp 383-387, Mazuren, 1985).
  • an electrode can be made by forming it into a film by means of anodic oxidation polymerization method onto a substrate which is previously provided with an electroconducting coating.
  • the thickness of an electrode to be formed on a substrate is not limited to a particular value, but, when the substrate is used as a light emitting plane, the thickness of the electrode is preferably within the range of from 1 nm to 300 nm, more preferably, within the range of from 5 to 200 nm so as to ensure transparency.
  • ITO is used on a substrate having an ITO film thickness in the range of from 10 nm (100 ⁇ ) to 1 ⁇ (10000 ⁇ ), preferably from 20 nm (200 ⁇ ) to 500 nm (5000 ⁇ ).
  • the sheet resistance of the ITO film is chosen in the range of not more than 100 ⁇ /cm 2 , preferably not more than 50 ⁇ /cm 2 .
  • Such anodes are commercially available from Japanese manufacturers, such as Geomatech Co. Ltd., Sanyo Vacuum Co. Ltd., Nippon Sheet Glass Co. Ltd.
  • an electronconducting or electrically insulating material can be used as substrate either an electronconducting or electrically insulating material.
  • a light emitting layer or a positive hole transporting layer is directly formed thereupon, while in case of using an electrically insulating substrate, an electrode is firstly formed thereupon and then a light emitting layer or a positive hole transporting layer is superposed.
  • the substrate may be either transparent, semi-transparent or opaque. However, in case of using a substrate as an indicating plane, the substrate must be transparent or semi-transparent.
  • Transparent electrically insulating substrates are, for example, inorganic compounds such as glass, quartz and the like, organic polymeric compounds such as polyethylene, polypropylene, polymethylmethacrylate, polyacrylonitrile, polyester, polycarbonate, polyvinylchloride, polyvinylalcohol, polyvinylacetate and the like.
  • inorganic compounds such as glass, quartz and the like
  • organic polymeric compounds such as polyethylene, polypropylene, polymethylmethacrylate, polyacrylonitrile, polyester, polycarbonate, polyvinylchloride, polyvinylalcohol, polyvinylacetate and the like.
  • semi-transparent electrically insulating substrates examples include inorganic compounds such as alumina, YSZ (yttrium stabilized zirconia) and the like, organic polymeric compounds such as polyethylene, polypropylene, polystyrene, epoxy resins and the like. Each of these substrates can be transformed into a semitransparent electroconducting substrate by providing it with an electrode according to one of the above-mentioned methods.
  • opaque electroconducting substrates are metals such as aluminum, indium, iron, nickel, zinc, tin, chromium, titanium, copper, silver, gold, platinum and the like, various electroplated metals, metallic alloys such as bronze, stainless steel and the like, semiconductors such as Si, Go, GaAs, and the like, electroconducting polymers such as polyaniline, polythiophene, polypyrrole, polyacetylene, polyparaphenylene and the like.
  • a substrate can be obtained by forming one of the above listed substrate materials to a desired dimension. It is preferred that the substrate has a smooth surface. Even, if it has a rough surface, it will not cause any problem for practical use, provided that it has round unevenness having a curvature of not less than 20 ⁇ m. As for the thickness of the substrate, there is no restriction as far as it ensures sufficient mechanical strength.
  • cathode materials which possess low work function such as alkali metals, earth alkaline metals, group 13 elements, silver, and copper as well as alloys or mixtures thereof such as sodium, lithium, potassium, calcium, lithium fluoride (LiF), sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-copper alloy, magnesium-aluminum alloy, magnesium-indium alloy, aluminum, aluminum-aluminum oxide alloy, aluminum-lithium alloy, indium, calcium, and materials exemplified in EP-A 499,011 such as electroconducting polymers e.g. polypyrrole, polythiophene, polyaniline, polyacetylene etc., preferably Mg/Ag alloys, LiF—Al or Li—Al compositions can be used.
  • electroconducting polymers e.g. polypyrrole, polythiophene, polyaniline, polyacetylene etc., preferably Mg/Ag alloys, LiF—Al or Li—Al composition
  • a magnesium-silver alloy or a mixture of magnesium and silver, or a lithium-aluminum alloy, lithium fluoride-aluminum alloy or a mixture of lithium and aluminum can be used in a film thickness in the range of from 10 nm (100 ⁇ ) to 1 ⁇ m (10000 ⁇ ), preferably from 20 nm (200 ⁇ ) to 500 nm (5000 ⁇ ).
  • Such cathodes can be deposited on the foregoing electron transporting layer by known vacuum deposition techniques described above.
  • a light-emitting layer can be used between the hole transporting layer and the electron transporting layer.
  • the light-emitting layer is prepared by forming a thin film on the hole transporting layer.
  • the vacuum deposition method As methods for forming said thin film, there are, for example, the vacuum deposition method, the spin-coating method, the casting method, the Langmuir-Blodgett (“LB”) method and the like.
  • the vacuum deposition method, the spin-coating method and the casting method are particularly preferred in view of ease of operation and cost.
  • the conditions under which the vacuum deposition is carried out are usually strongly dependent on the properties, shape and crystalline state of the compound(s).
  • optimum conditions are usually as follows: temperature of the heating boat: 100 to 400° C.; substrate temperature: —100 to 350° C.; pressure:1.33 ⁇ 10 4 Pa (1 ⁇ 10 2 Torr) to 1.33 ⁇ 10 4 Pa (1 ⁇ 10 ⁇ 6 Torr) and deposition rate: 1 pm to 6 nm/sec.
  • the thickness of the light emitting layer is one of the factors determining its light emission properties. For example, if a light emitting layer is not sufficiently thick, a short circuit can occur quite easily between two electrodes sandwiching said light emitting layer, and therefor, no EL emission is obtained. On the other hand, if the light emitting layer is excessively thick, a large potential drop occurs inside the light emitting layer because of its high electrical resistance, so that the threshold voltage for EL emission increases. Accordingly, the thickness of the organic light emitting layer is limited to the range of from 5 nm to 5 ⁇ m, preferably to the range of from 10 nm to 500 nm.
  • the coating can be carried out using a solution prepared by dissolving the composition in a concentration of from 0.0001 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide, dichloromethane, dimethylsulfoxide and the like. If the concentration exceeds 90% by weight, the solution usually is so viscous that it no longer permits forming a smooth and homogenous film. On the other hand, if the concentration is less than 0.0001% by weight, the efficiency of forming a film is too low to be economical. Accordingly, a preferred concentration of the composition is within the range of from 0.01 to 80% by weight.
  • any polymer binder may be used, provided that it is soluble in the solvent in which the composition is dissolved.
  • polymer binders are polycarbonate, polyvinylalcohol, polymethacrylate, polymethylmethacrylate, polyester, polyvinylacetate, epoxy resin and the like.
  • the fluidity of the solution is usually so low that it is impossible to form a light emitting layer excellent in homogeneity.
  • the preferred ratio of the polymer binder to the composition is chosen within the range of from 10:1 to 1:50 by weight, and the solid content composed of both components in the solution is preferably within the range of from 0.01 to 80% by weight, and more preferably, within the range of 0.1 to 60% by weight.
  • organic hole transporting compounds such as polyvinyl carbazole
  • Q 1 and Q 2 each represent a hydrogen atom or a methyl group
  • T and T 1 stand for an organic radical
  • R x , R y and R z stand for an organic radical, and the like can be used.
  • Compounds to be used as a positive hole transporting material are not restricted to the above listed compounds. Any compound having a property of transporting positive holes can be used as a positive hole transporting material such as triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivative, pyrazolone derivatives, phenylene diamine derivatives, arylamine derivatives, amino substituted chalcone derivatives, oxazole derivatives, stilbenzylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, copolymers of aniline derivatives, PEDOT (poly (3,4-ethylenedioxy-thiophene)) and the derivatives thereof, electro-conductive oligomers, particularly thiophene oligomers, porphyrin compounds, aromatic tertiary amine compounds, stilbenzyl amine compounds etc.
  • PEDOT poly (3,4-ethylenedioxy-thiophene
  • aromatic tertiary amine compounds such as N,N,N′,N′-tetraphenyl-4,4′-diaminobiphenyl, N,N-diphenyl-N,N′-bis(3-methylphenyl)-4,4′-diaminobiphenyl (TPD), 2,2′-bis(di-p-torylaminophenyl)propane, 1,1′-bis(4-di-torylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenyl-methane, N,N′-diphenyl-N,N′-di(4-methoxyphenyl)-4,4′-diaminobiphenyl, N,N,N′,N′-tetraphenyl-4,4′-diamino
  • 4,4′-bis[N-(1-naphtyl)-N-phenylamino]biphenyl disclosed in U.S. Pat. No. 5,061,569 and the compounds disclosed in EP-A 508,562, in which three triphenylamine units are bound to a nitrogen atom, such as 4,4′,4′′-tris[N-(3-methylphenyl)-N-phenylamino]tri-phenylamine, can be used.
  • a positive hole transporting layer can be formed by preparing an organic film containing at least one positive hole transporting material on the anode.
  • the positive hole transporting layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, ink jet printing method, the LB method and the like. Of these methods, the vacuum deposition method, the spin-coating method and the casting method are particularly preferred in view of ease and cost.
  • the conditions for deposition may be chosen in the same manner as described for the formation of a light emitting layer (see above). If it is desired to form a positive hole transporting layer comprising more than one positive hole transporting material, the coevaporation method can be employed using the desired compounds.
  • the layer can be formed under the conditions described for the formation of the light emitting layer (see above).
  • a smoother and more homogeneous positive hole transporting layer can be formed by using a solution containing a binder and at least one positive hole transporting material.
  • the coating using such a solution can be performed in the same manner as described for the light emitting layer.
  • Any polymer binder may be used, provided that it is soluble in the solvent in which the at least one positive hole transporting material is dissolved. Examples of appropriate polymer binders and of appropriate and preferred concentrations are given above when describing the formation of a light emitting layer.
  • the thickness of the positive hole transporting layer is preferably chosen in the range of from 0.5 to 1000 nm, preferably from 1 to 100 nm, more preferably from 2 to 50 nm.
  • organic hole transporting compounds such as metal-free phthalocyanine (H 2 Pc), copper-phthalocyanine (Cu—Pc) and their derivatives as described, for example, in JP64-7635 can be used.
  • H 2 Pc metal-free phthalocyanine
  • Cu—Pc copper-phthalocyanine
  • JP64-7635 organic hole transporting compounds
  • some of the aromatic amines defined as hole transporting materials above, which have a lower ionisation potential than the hole transporting layer, can be used.
  • a hole injection layer can be formed by preparing an organic film containing at least one hole injection material between the anode layer and the hole transporting layer.
  • the hole injection layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, the LB method and the like.
  • the thickness of the layer is preferably from 5 nm to 5 ⁇ m, and more preferably from 10 nm to 100 nm.
  • the electron transporting materials should have a high electron injection efficiency (from the cathode) and a high electron mobility.
  • the following materials can be exemplified for electron transporting materials: tris(8-hydroxyquinolinato)-aluminum(III) and its derivatives, bis(10-hydroxybenzo[h]quinolinolato)beryllium(II) and its derivatives, oxadiazole derivatives, such as 2-(4-biphenyl)-5-(4-tert.-butylphenyl)-1,3,4-oxadiazole and its dimer systems, such as 1,3-bis(4-tert.-butylphenyl-1,3,4)oxadiazolyl)biphenylene and 1,3-bis(4-tert.-butylphenyl-1,3,4-oxadiazolyl)phenylene, dioxazole derivatives, triazole derivatives, coumarine derivatives, imidazopyridine derivatives, phenanthro
  • An electron transporting layer can be formed by preparing an organic film containing at least one electron transporting material on the hole transporting layer or on the light-emitting layer.
  • the electron transporting layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, the LB method and the like.
  • the positive hole inhibiting materials for a positive hole inhibiting layer have high electron injection/transporting efficiency from the electron transporting layer to the light emission layer and also have higher ionisation potential than the light emitting layer to prevent the flowing out of positive holes from the light emitting layer to avoid a drop in luminescence efficiency.
  • phenanthroline derivatives e.g. bathocuproine (BCP)
  • BCP bathocuproine
  • the positive hole inhibiting layer can be formed by preparing an organic film containing at least one positive hole inhibiting material between the electron transporting layer and the light-emitting layer.
  • the positive hole inhibiting layer can be formed by the vacuum deposition method, the spin-coating method, the casting method, ink jet printing method, the LB method and the like.
  • the thickness of the layer preferably is chosen within the range of from 5 nm to 2 ⁇ m, and more preferably, within the range of from 10 nm to 100 nm.
  • a smoother and more homogeneous electron transporting layer can be formed by using a solution containing a binder and at least one electron transporting material.
  • the thickness of an electron transporting layer is preferably chosen in the range of from 0.5 to 1000 nm, preferably from 1 to 100 nm, more preferably from 2 to 50 nm.
  • the host chromphore is a diketopyrrolopyrrole having a photoluminescence emission peak at 500 to 720 nm, preferably 520 to 630 nm, most preferred 540 to 600 nm.
  • the host chromphore is preferably a diketopyrrolopyrrole of formula III.
  • the light-emitting compositions have a fluorescence emission maximum in the range of from 500 to 780, preferably from 520 to 750, more preferred from 540 to 700 nm. Further, the inventive compounds preferably exhibit an absorption maximum in the range of 450 to 600 nm.
  • the light-emitting compositions usually exhibit a fluorescence quantum yield (“FQY”) in the range of from 1>FQY ⁇ 0.3 (measured in aerated toluene or DMF). Further, in general, the inventive compositions exhibit a molar absorption coefficient in the range of from 5000 to 100000.
  • FQY fluorescence quantum yield
  • Another embodiment of the present invention relates to a method of coloring high molecular weight organic materials (having a molecular weight usually in the range of from 10 3 to 10 7 g/mol; comprising biopolymers, and plastic materials, including fibres) by incorporating therein the inventive compounds or compositions by methods known in the art.
  • high molecular weight organic materials having a molecular weight usually in the range of from 10 3 to 10 7 g/mol; comprising biopolymers, and plastic materials, including fibres
  • inventive compounds and compositions can be used, as described, for example, for DPP compounds in EP-A-1087005, for the preparation of
  • Another preferred embodiment concerns the use of the inventive compounds and compositions for color changing media.
  • inventive compounds or compositions are useful for EL materials for the above category (i) and, in addition, for the above mention technique (ii). This is because the invented compounds or compositions can exhibit strong photoluminescence as well as electroluminescence.
  • Technique (ii) is, for example, known from U.S. Pat. No. 5,126,214, wherein EL blue with a maximum wavelength of ca. 470-480 nm is converted to green and red using coumarin, 4 (dicyanomethylene)-2-methyl-4-(p-dimethylaminostyryl)-4H-pyran, pyridine, rhodamine 6G, phenoxazone or other dyes.
  • inventive compounds or compositions are useful for EL materials for the above category (iii) as an element of white luminescent in combination of other compensatory electroluminescence to construct white luminescent. This is because compounds or compositions can exhibit strong photoluminescence as well as electroluminescence.
  • Particularly preferred high molecular weight organic materials are, for example, cellulose ethers and esters, e.g. ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins or synthetic resins (polymerization or condensation resins) such as aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, poly-urethanes, polyester, ABS, ASA, polyphenylene oxides, vulcanized rubber, casein, silicone and silicone resins as well as their possible mixtures with one another.
  • cellulose ethers and esters e.g. ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate
  • natural resins or synthetic resins polymerization or condensation resins
  • aminoplasts in particular urea/formal
  • organic materials in dissolved form as film formers, for example boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins as well as acrylic resins.
  • film formers for example boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins as well as acrylic resins.
  • Said high molecular weight organic materials may be obtained singly or in admixture, for example in the form of granules, plastic materials, melts or in the form of solutions, in particular for the preparation of spinning solutions, paint systems, coating materials, inks or printing inks.
  • inventive compounds and compositions are used for the mass coloration of polyvinyl chloride, polyamides and, especially, polyolefins such as polyethylene and polypropylene as well as for the preparation of paint systems, including powder coatings, inks, printing inks, color filters and coating colors.
  • Illustrative examples of preferred binders for paint systems are alkyd/melamine resin paints, acryl/melamine resin paints, cellulose acetate/cellulose butyrate paints and two-pack system lacquers based on acrylic resins which are crosslinkable with polyisocyanate.
  • composition comprising
  • inventive (fluorescent compounds) of formula I or the inventive compositions may advantageously be used in admixture with fillers, transparent and opaque white, colored and/or black pigments as well as customary luster pigments in the desired amount.
  • the corresponding high molecular weight organic materials such as binders, synthetic resin dispersions etc. and the inventive compounds or compositions are usually dispersed or dissolved together, if desired together with customary additives such as dispersants, fillers, paint auxiliaries, siccatives, plasticizers and/or additional pigments or pigment precursors, in a common solvent or mixture of solvents.
  • customary additives such as dispersants, fillers, paint auxiliaries, siccatives, plasticizers and/or additional pigments or pigment precursors, in a common solvent or mixture of solvents. This can be achieved by dispersing or dissolving the individual components by themselves, or also several components together, and only then bringing all components together, or by adding everything together at once.
  • a further embodiment of the present invention relates to a method of using the inventive compounds or compositions for the preparation of dispersions and the corresponding dispersions, and paint systems, coating materials, color filters, inks and printing inks comprising the inventive compositions.
  • a particularly preferred embodiment relates to the use of the inventive compounds, or compositions for the preparation of fluorescent tracers for e.g. leak detection of fluids such as lubricants, cooling systems etc., as well as to fluorescent tracers or lubricants comprising the inventive compositions.
  • the inventive compounds or compositions are mixed with the high molecular weight organic materials using roll mills, mixing apparatus or grinding apparatus.
  • the pigmented material is subsequently brought into the desired final form by conventional processes, such as calandering, compression molding, extrusion, spreading, casting or injection molding.
  • the high molecular weight organic materials and the inventive compounds or compositions alone or together with additives, such as fillers, other pigments, siccatives or plasticizers, are generally dissolved or dispersed in a common organic solvent or solvent mixture.
  • additives such as fillers, other pigments, siccatives or plasticizers
  • the present invention additionally relates to inks comprising a coloristically effective amount of the pigment dispersion of the inventive compositions.
  • the weight ratio of the pigment dispersion to the ink in general is chosen in the range of from 0.001 to 75% by weight, preferably from 0.01 to 50% by weight, based on the overall weight of the ink.
  • the color filters can be coated for example using inks, especially printing inks, which can comprise pigment dispersions comprising the inventive compositions or can be prepared, for example, by mixing a pigment dispersion comprising an inventive composition with chemically, thermally or photolytically structurable high molecular weight organic material (so-called resist).
  • the subsequent preparation can be carried out, for example, in analogy to EP-A 654 711 by application to a substrate, such as a LCD (liquid crystal display), subsequent photostructuring and development.
  • pigment dispersions comprising an inventive compound or composition which possess non-aqueous solvents or dispersion media for polymers.
  • the present invention relates, moreover, to toners comprising a pigment dispersion containing an inventive compounder composition or a high molecular weight organic material pigmented with an inventive composition in a coloristically effective amount.
  • the present invention additionally relates to colorants, colored plastics, polymeric ink particles, or non-impact-printing material comprising an inventive composition, preferably in the form of a dispersion, or a high molecular weight organic material pigmented with an inventive composition in a coloristically effective amount.
  • a coloristically effective amount of the pigment dispersion according to this invention comprising an inventive composition denotes in general from 0.0001 to 99.99% by weight, preferably from 0.001 to 50% by weight and, with particular preference, from 0.01 to 50% by weight, based on the overall weight of the material pigmented therewith.
  • inventive compositions can be applied to colour polyamides, because they do not decompose during the incorporation into the polyamides. Further, they exhibit an exceptionally good lightfastness, a superior heat stability, especially in plastics.
  • the organic EL device of the present invention has significant industrial values since it can be adapted for a flat panel display of an on-wall television set, a flat light-emitting device, a light source for a copying machine or a printer, a light source for a liquid crystal display or counter, a display signboard and a signal light.
  • the compounds and compositions of the present invention can be used in the fields of an organic EL device, an electrophotographic photoreceptor, a photoelectric converter, a solar cell, an image sensor, and the like.
  • a glass substrate (manufactured by Geomatek Co., a product prepared by electron beam vapor deposition method) on which an ITO transparent electroconductive film had been deposited up to a thickness of ca. 150 nm is cut into a size of 10 ⁇ 20 mm, and etched.
  • the substrate thus obtained is subjected to ultrasonic washing with detergent water for 15 minutes, and then washing with pure water. Subsequently, the substrate is subjected to ultrasonic washing with acetone for 15 minutes, and then dried.
  • the substrate thus obtained is subjected to a plasma treatment for half an hour and placed in a vacuum vapour deposition apparatus, and the apparatus is evacuated until the inner pressure reached 1 ⁇ 10 ⁇ 5 Pa or less.
  • a Alq 3 layer is vapor-deposited to form an electron transporting/injection layer having a thickness of 30 nm.
  • LiF was deposited on Alq3 layer with a thickness of 0.5 nm.
  • a Mg—Ag alloy (10:1) is vapor-deposited to form a cathode having a thickness of 150 nm, whereby an element having a size of 5 ⁇ 5 mm square is prepared.
  • the luminescent peak wavelength and emission intensity of the luminescent element thus obtained is summarized in Table 1.
  • Example 6 is repeated, except that the emitting material of example 6 is replaced by the emitting materials as described in table 1.
  • Example 8 is repeated, except that the compound below (A-3; Example 81 of EP-A-1087006) is used as the light emitting material.
  • the maximum luminance is 5260 Cd/m 2 .

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